Apparatus for making chemical substitutions



Jan. 28, 1941. SLAYTER 2,229,679

APPARATUS FOR MAKING CHEMICAL SUBSTITUTIONS ori inal Filed April 28, 1938 INVEN TOR.

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ATTORNEY Patented Jan. 28, 1941 UNITED STATES APPARATUS MAKING CHEMICAL SUBSTITUTIONS Games Sla'ytcr, Newark, Ohio, assignor to-Electro ic Research Corporation, Newark, Ohio, a

,corporation of Ohio Original application April 28, 1938, Serial No. 204,885. Divided and this application October 25, 1938, Serial No. 236,960

7 Claims.

My invention relates broadly to an apparatus for accelerating chemical substitutions by the discharge oi electricity from. conducting points at high voltage in chemicals.

This application is a division of my application Serial No. 204,885, flied April 28, 1938, for Method of making chemical substitutions.

One of the objects of my invention is to provide an apparatus for electrically accelerating substitutions in chemicals of all combinations and permutations generally such as for example, in hydrocarbons the substitution 'of chlorine, bromine, amino, and other groups.

Another object of my invention is to provide an apparatus for'carrying out a method of promoting catalytic reaction by the discharge of electricity from conducting points at high voltage in chemicals. 7

Still another object of my invention is to provide an apparatus for electrically accelerating substitutions in chemical baths by means of electrical discharges in which incipient sparks A further object of my invention is to provide an apparatus for promoting substitutions in chemical solutions in which a gaseous substituent is introduced into the chemical under con- .ditions of electrical stress but in which sparking is suppressed.

A still i'urther object of my invention is to provide an apparatus for accelerating chemical changes by electric discharges in chemical solutions while suppressing a condition of sparking.

Other and further objects of my invention reside in the apparatus for promoting substitutions in chemical solutions as set forth more fully in the specification hereinafter following by reference to theaccompanying drawing in which:

Figure 1 schematically illustrates one form of apparatus for promoting substitutions in chemical solutions in accordance with my invention. when the substituent is capable of being dissolved, mixed or suspended in the solution; Fig. 2 is a schematic view showing the apparatus used in carrying out my invention when the substituent used is in the gaseous form; Fig. 3 is an enlarged fragmentarysectional view I showing one manner of forming the hollow tubular electrode employed in the arrangement of 2; and Fig. 4 is a fragmentary sectional view showing the manner of finishing the end of the tubular electrode. The discharge of electricity from conducting points at high voltage in chemical solutions can 55 be made to produce regions of high electric stress and molecular dissociation by electron bombardment. Discharge under a. nonconducting liquid ordinarily is disruptive in character and is a spark through the liquid accompanied by much heat. It a high resistance is put in series with the discharge point, an incipient spark is arrested so that the principal effect is to produce electron bombardment in vapor phase through short distances near the point.

. My invention is directed to an electrical apparatus for promoting substitutions in chemical solutions by producing chemical reactions, 111-, cluding all combinations and permutations of the classes:

XY-i-HY XY-i-H:

IEH-HY XY+HX XY+HZ xz+HY xr+wz -9 XZ+WY where X, Y, Z, and W may each or in any combinations be atoms or radicals of all types and classes.

When efiecting substitutions in hydrocarbons of chlorine, bromine, amino, and other groups, either of two methods may be used in treating hydrocarbons of the types:

RH-i-Hx RX+H2 or r r RH-I-n RX-i-HX where R is the hydrocarbon radical so RH is the hydrocarbon: X is a substituent such as Cl, Br, I, F, N02, S02, SH, H, etc.

' The first method is used it the substituent can be dissolved, mixed or suspended, as a colloid, in the hydrocarbon. In this case the reaction is promoted as a result of the discharge from the point. The second method is adapted for use if the substituent must be used in the gaseous fornn In this case, the discharge may be drawn from a fine hollow tube such as a hypodermic needle the end of which has been ground square, then polished smooth-and rounded. The gaseous substituent is then forced through the tube slowly enough for the gas to break into a train of fine bubbles in the hydrocarbon and thus avoid sparking through the gas alone.

This process is valuable for the accomplishment of substitutions now requiring expensive l catalysts, catalysts sensitive to poisons, or catalytic reactions giving poor yields. Methods for producing continuous operation can easily be devised ior each reaction because a constriction in the flow, of the llquid,1ust back of the dlscharg- If,"

ing point does not aflect the electrical performance of the discharge.

Referring to the drawing in detail, reference character I designates a tank in which the chemical solution 2 is contained. The tank I is suitably formed to permit the passage of electrodes indicated at 3 and 4, submerged beneath the surface of the chemical solution 2. The electrodes 3 and 4 are so mounted in the tank I that a fluid tight connection is made between the electrodes and the side walls of the tank at 5 and 6 by suitable liquid tight cement or gaskets. The electrode 3 is tapered to a discharge point indicated at I. The electrode 4 is provided with a flat target area 8. A power'supply circuit is connected with electrodes 3 and 4 through transformer system 9 and a primary winding Ill and secondary winding ll. Primary winding Ill may be connected with any suitable power source of alternating current. Secondary winding H has high resistance I2 connected in series therewith and in series with the binding posts l4 and I5 on electrodes 3' and 4 respectively. The high voltage applied across electrodes 1 and 8 within the chemical solution 2 produces a region of high electric stress and molecular dissociation by electron bombardment. However, there is no disruptive discharge between electrodes I and 8 and any incipient spark is arrested by reason of the characteristics of the circuit containing the discharge electrodes resulting from the introduction of high resistance l2. In this arrangement the substituent is dissolved, mixed or suspended as a colloid in the chemical solution 2 and the substitution is effected in the region of high electric stress and molecular dissociation by electron bombardment in the immediate area of discharge point 1 and electrode 8.

Where, however, the substituent must be used in a gaseous form, I provide an arrangement as illustrated in Fig. 2 wherein the electrode I6 is employed in the form of a fine hollow tube, such as a hypodermic needle whose end I! has been transversely cut as represented in Fig. 3 along the line 23. The cut end I! of the tube I6 is then rounded as indicated at 24 in Fig. 4, and polished smooth, forming the tubular discharge electrode. The gaseous substituent is contained in pressure tank I8 or its equivalent from which it is supplied to control valve I3 and pipe line to the fine hollow tube electrode 1 i. The gaseous substituent is forced through tube'lG slowly enough for the gas to break into a train of fine bubbles in the chemical solution 2 and thus avoid sparking through the gas alone. That is to say, the train of fine bubbles indicated at 2| does not permit an accumulation of gases in the region about the smooth rounded end 24 of electrode [6, so that a break-down of the discharge resulting in sparking does not occur. A region of high electric stress and molecular dissociation exists between electrodes l6 and 8 but there is no spark discharge.

The tubular electrode l6 has a binding post 22 thereon which also serves as a coupling member to the supply pipe 20 for delivery of gas through the tube I6. An energization circuit including secondary winding I l and high resistance l2 connects to'electrodes 8 and I5 in the same manner as described in connection with Fig. 1.

The process of substitution carried out by the apparatus of my invention does not involve expensivecatalysts, or catalysts sensitive to poisons, or catalytic reactions giving poor yields. The discharge of the gas is controlled by valve l 9 so that the flow is so restricted through tubular discharge member l6 that sparking between electrodes [6 and 8 is not permitted. The rate or velocity of flow of the gaseous substituent in the direction of the target electrode 8 is varied and controlled by valve I3. I

The region of high dissociation hereinbefore described is such as accompanies a non-disruptive discharge such as a dark discharge or a brush or a glow discharge, all of which are forms of silent electric discharge as differentiated from disruptive spark and are discharges which produce sudden noises due to the disruptive eiiects of thedischarges. In the practice of my invention, therefore, I may employ any form of non-disruptive discharge, and wherever'in the claims I specify silent discharge it will be understood that any discharge nonelectric stress and molecular to an apparatus for making substitutions in all chemical solutions including all combinations and permutations of such solutions generally.

It will be entirely clear that I may employ more than one discharge point and more than one discharge tube in the arrangement of my invention.

While I have described the apparatus of my invention in certain preferred forms, I desire that it be understood that my invention may be carried out by modified forms of the apparatus of my invention without departing from the spirit of the appended claims.

What I claim as new and desire to secure by Letters Patent of the United States is as follows:

1. In an apparatus for making chemical substitutions a container for a liquid mixture of a chemical solution and the substituent, means for producing a silent electric discharge including a pair of electrodes in said container submerged in the mixture therein, one of said electrodes comprising a sharp edged discharge electrode directed toward and spacially related to the other electrode in minimum capacitive relation thereto, means for impressing a high voltage between said discharge electrode and said other electrode, and means cooperative with the last said means and having a resistance suflicient in relation to the capacitance of said discharge electrode to prevent disruptive discharge between said discharge electrode and said other electrode; said apparatus being operative to produce a region of high electric stress and molecular dissociation in the liquid mixture between said electrodes wherein the chemical substitution is accelerated.

2. In an apparatus for making chemical substitutions a container for a liquid mixture of a chemical solution and the substituent, means for producing a silent electric discharge including a pair of electrodes extending substantially horizontally through the walls of said container, means for supporting said electrodes in the walls of said container and for preventing seepage of the mixture through the walls of said container at the point of entry of said electrodes, one of said electrodes comprising a sharp edged discharge electrode directed toward and spacially related age between said electrodes for establishing a si-.

lent electric discharge therebetween and through said mixture, and means cooperative with the last said means and having a resistance suflicient in relation to the capacitance oi said discharge electrode to prevent disruptive discharge between I in the mixture therein, one of said electrodes said electrodes.

3. In an apparatus for making chemical substitutions a container tor a liquid mixture of a chemical solution and the substituent, means for producing a silent electric discharge including a pair 01' electrodes in said container submerged in the mixture therein, one of said electrodes comprising a sharp edged discharge electrode and the other of said electrodes comprising a plate extending on a plane substantially normal to the plane of the first mentioned electrode, said discharge electrode thereby having a minimum electrical capacitance with respect to said plate, means for impressing a high diiIerence or potential across said electrodes, and means cooperative with thelast said means and having a resistance sumcient in relation to the capacitance of said discharge electrode to prevent disruptive discharge between said electrodes; said apparatus being operative to produce a region oi high electric stress and molecular dissociation in the liquid mixture between said' electrodes wherein the chemical substitution is accelerated.

4. In an apparatus for making chemical substitutions a container for a liquid mixture of a chemical solution and the substituent, means for producing a silent electric discharge including a pair of electrodes in said container submerged in the mixture therein, one of said electrodes comprising a discharge point and the other of said electrodes comprising a plate spacially related to the discharge point, said discharge point having a minimum electrical capacitance with respect to said plate, a circuit for impressing a high difference of potential across said electrodes, and a resistor interposed in said circuit for controlling said circuit and having a resistance cooperative with the capacitance of said discharge point so that disruptive discharge between said electrodes is prevented; said apparatus being operative to produce a region of high electric stress and molecular dissociation in the liquid mixture between said electrodes wherein the chemical substitution is accelerated.

, 5.In an apparatus for making chemical substitutions av container for a liquid mixture of a chemical solution and thesubstituent, means for producing a silent electric discharge including a pair of electrodes in said container submerged comprising a discharge point and the other oi. said electrodes comprising a target plate spacially related to and operatively aligned with the discharge point, said discharge point having a minimum electrical capacitance with respect to said plate, a source of alternating current, a high voltage transformer having its primary winding connected with said source and its secondary wind- .ing connected with -said electrodes for impressing high potential across said electrodes for establishing a silent electric discharge therebetween and through said mixture, and means in circuit with said secondary winding and said electrodes and having a resistance sufficient in relation to the capacitance of said discharge point to prevent disruptive discharge between said electrodes.

6.'In an apparatus for making chemical substitutions a container for a liquid chemical solution, means for producing a silent electric discharge including a pair of electrodes in said container submerged in the solution therein, one of said electrodes comprising a plate and the other of said electrodes comprising a sharp edged tubular member directed substantially horizontally toward'and specially related to said plate in min trodes for impressing high voltage therebetween,

means connected in circuit with said secondary winding and said electrodes and having a resistance sufllcient in relation to the capacitance of said tubular-member to prevent disruptive discharge therebetween, and means for introducing a gaseous substituent through said tubular member to a limited extent toward said plate; said apparatus being operative to produce a silent electric discharge irom said tubular electrode into the held of which the gaseous substituent is directly introduced.

7. In an apparatus for making chemical-substitutions a container for a liquidchemical solution, means for producing a silent electric discharge including a pair of electrodes in said container submerged in the solution therein, one of said electrodes comprising a plate and the other of said electrodes comprising a sharp edged tubular member directed substantially horizontally toward and spacially related to the plate electrade in minimum capacitive relation thereto, a source of alternating current, a transformer having a primary winding connected with said source and a secondary winding connected in circuit with said electrodes for impressing a high voltage across said electrodes, a resistor interposed in series in said circuit and having a resistance suflicient in relation-to the capacitance rectly introduced and wherein the chemical substitution is accelerated.

GAMES SLAY'IER. 

